9.10 diamino anthracene and its nu-substitution products



Patented July 11, 1933 UNITED STATESE'PA'TENT {HOFFI'CE MAX ALBERT KUNZ, on MANNI-IEIM,A1\TD armors STROH AND ERMANN DIMROTH, on LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., on NEW YORK, N. Y.,n oonronn'rion or DELAWARE 9.10 DIAMINO ANTHRACENE Ann rrs n-sussrrrn'rron rnonucrs No Drawing. Application filed April 8, 1931, Serial No. 528,702, and in Germany December 1, 1928 The present invention relates to new anthracene derivatives substituted in the 9 and 10 positions. a I

We have found that 9.10-diaminoanthracene and its substitution products having the following general structure: 7

in which X is hydrogen or an acyl group, and Y hydrogen, an acyl or an aryl group in which latter case X must be hydrogen, are for the most part intensively colored compounds suitable as pigments and also as intermediate products for the preparation of dyestuffs. They fluoresce when exposed to ultra-violet rays and are readily decomposed to anthraquinone and its substitution products when heated in sulphuric acid of from to per cent strength with oxidizing agents. I

Those of the aforesaid new products as contain an aliphatic carboxylic'acid radicle, such'as for example a formyl or acetyl radicle, attached to the amino group are best obtained by causingan anthraquinone to react with an aliphatic carboxylic acid amide. This reaction is broughtabout by heating the reacting components. The unsubstituted 9.10-diform'yl di-imino-anthracene. obtained in this manner corresponds to, the formula .1 DH Y9 The products obtained by condensation with amides of higher molecularaliphatic acids correspond to the said formula except that alkyl groups are connected to the carbon atoms instead of the hydrogenatoms.

The free 9.10 diaminoanthracenes of the hydrogen atoms of the amino groups aroreplacedby acyl radicles either aliphatic or aromatic, or one hydrogen atom of each of the amino groups arereplacedby arylradicles are readily obtained by causing aromatic amines, organic acid radi'cles or organic acid anhyd rides to react with the aforesaid 9.10- diforinyl di-iminoanthracenes. The reaction is brought about by simply heating the components, if desired in an indifferent organic diluentfsuchas for example nitrobenzene. /Vhen employing an aromatic amine as re actingcomponent it is advisable to add small amounts of asalt of an amine, for example aniline hydrochloride, to the reaction mixture, in case an organic acid halide or anhydride is used as reacting component small amounts of an acid binding agent, such as sodium acetate, may be added.

Another method 1 of producing 9.10-diaminoanthracenes in which one hydrogen atom of each amino group is replaced by an aryl group consists in reducing an anthraquinone-SlO-diahil. These latter compounds may be prepared the manner described in Liebigs Annalen der Chemie Vol. 396,'page 17 8, or by condensing anthraquinone or a substitution product thereof with a primary aromatic amine with the aid of a condensing metal halide, such as far example aluminium chloride, Zinc chloride and the like. The

reduction of theaforesaid anthraquinone- 9.10-dianils may be carried out in alkaline or acid media. The anthraqu1none-9.lO-dianils need not be isolated and then reduced, but reducing agents, such as for example zinc dust may be added to the reaction mixture during the condensation of an anthraquinone and a primary aromatic amine with the 'a1d of aluminium chlorideand the like- The following examples will furtherillus-v trate the nature of the invention butthe invention is not restricted to these The parts'are by weight.

Example 1 100 parts of anthraquinone and 500 parts of formamide are kept gently boiling, while stirring, for 4 hours. The reactionproduct is filtered from the hot reaction mixture and.

washed with water and ethyl alcohol. It is obtained in. a yield'about to. of that required by theory and according to analysis is a 9.10-diformyl di-iminoanthracene corresponding to the formula is filtered off. 'The reaction product is N.N'.

diformyl-9.10'diamino 2 chloroanthracene corresponding to the formula 111 i 7 11d=ox It is practically insoluble in most organic solvents but soluble in a solution of caustic potash in methyl alcohol.

E aampZe 3 200 parts of ground caustic potash are dissolved at room temperature in 4:00parts of methanol whereupon 60 parts of the product obtained according to Example 1 are introduced into the reaction .mixturewhich is then boiled for one hour. On cooling the product examples.

crystallizes in brown red needles which are filtered off. It may be recrystallized from amyl acetate and is most probably 9.10-diaminoanthracene which on heating with sulphuric acid of 70 per cent strength with manganese dioxide is decomposed into anthraquinone.

E aample .4

2 parts of the product obtained according to Example 1 are dissolved in a solution of 3 parts of caustic potash in 10 parts of methanol, whereupon a solution of 1 part of ammonium chloride in Qparts of water are added and the reaction mixture kept boiling for 1 hour. On cooling the reaction product separates from the solution. Itv is 9-N- formyl-S).10diaminoanthracene corresponding to the formula 1 Example 5 5 parts of the product obtained from 2- chloroanthraquinone and formamide in the manner described in Example 2 are introduced. into a solution of 20 parts of caustic potash in lO parts of methanol whereupon the reactioirmixture is kept boiling for about one hour. On cooling the product separates from the reaction mixture as a red yellow powder. It is most probably the 2-chloro- 9.10-diaminoanthracene which may be crystallized from organic solvents such as xylene. 1..

Example 6 1 part of the condensation product obtained accordlng toExample-l is heated to boiling for half an hour with lpart ot' aniline hydrochloride and 10 parts of aniline. After cooling the reaction product is filtered off,

I washed with ethyl alcohol and hot water. The yieldam ounts to about 120 per cent of the initial material. The product has the form of intensively yellow coloured needles which maybe recrystallized from trichlorobenzene and is most, probably the 9.10-dianilinoanthracene. The composition of the product is 86.9 per cent O, 5.7 per cent H, and 7.74 per cent N, the calculated composition of 9.10-dianilinoanthracene (O H N being 86.63 per cent O, 5.60 per cent H and 7.77 per cent N.

' Ea'ample '7 4 parts of the product obtained according to Example 1 are heated at 100 O. with 40 parts of nitrobenzene, whereupon (3 parts oi benzoyl chloride are dropped into the reaction mixture which is heated'to boiling for one hour. The yellow'needlesseparating from the reaction mixture on cooling dissolve' in a solution of caustic potash in methanol to give a brown yellow coloration. According to analysis the product is NN-dibenzoyl-9.10-diaminoanthracene corresponding to the formula Example 8 1 part of the product obtained according to Example 1 is heated for about 2 hours, while stirring, to boiling with 1 part of ptoluidine hydrochlorideand 10 parts of p- I ,H-N My Example 9' 1 part of the product obtained according to Example 1 is heated to boiling for several.

-. hours with 5 parts of acetic acid anhydride.

The new compound separates from the reaction mixture on cooling and may readily be recrystallized from glacial acetic acid or chloroform. It shows an intensive blue fluorescence when exposed to ultraviolet light. According to analysis it is N.N- tetraacetyl-Q.lO-diamino-anthracene corresponding to the formula CH3 on: o=hN =o Thereaction can be promoted by the addition of 1 part of sodium acetate. In both cases the yields are practically quantitative.

.- Ewample 10 1 part of the product obtained according to Example 1 isheated to boiling for several hours with 3 parts of phthalic acid anhydride and 6 parts'of nitrobenzene. On cooling the reaction product separates out from the reaction mixture as a faintly coloured powder from which unconverted initial material may be extractedbymeans of solvents, such as for example toluene, benzene and xylene. The product may be recrystallized from nitrobenzene or xylene. Its solutions show a blue fluorescence. It is supposed that the re action'product consists to a substantial degree of 9.10-di-phthalyliminoanthracene corresponding to the formula tits, 5 Example 11 1 part of the condensation product of 2- chloroanthraquinone and formamide obtained in the manner described in Example 2 is heated to boiling for several hours with H: OH:

- Example 12 2 parts of aluminium chloride are introduced while stirring into a suspension of 1 part of anthraquinone in 10 parts of aniline whereupon the reaction mixture is stirred for from 1 to 2 hours at between 50 and 60 C. The reaction mixture is freed from the excess of aniline by means of. an alkaline steam distillation. The reaction product is then filtered ofl and'ma-y" further be purified by recrystallization from trichloro-benzene or acetic acid anhydride. It forms yellow crystals dissolving in 60 per cent sulphuric acid to give a red solution. On'allowing the sulphuric acid solution to stand, morequickly on warming, the product is de compose'dand anthraquinone separates out. I l

The reaction product obtained in the manner described in the foregoing paragraph is introduced into 20 parts of water to which parts of a caustic soda solution of 40 Be;

p the product is introduced into a solution of 7 parts of stannous chloride in 75 parts of aniline, whereupon the mixture is heated to boiling for a short time.- On pouring the reaction mixture into dilute acid the reduction product separates out in the form of a brilliant yellow precipitate which may be recrystallized from amyl alcohol. The product is 9.10-di-o-chloranilino-l-chloroanthracene corresponding to the formula 7 v Ewmple 16 2 parts of anhydrous aluminium chloride and 1.2 parts of anthraquinone-fl-sulphonic acid sodium salt are added to parts of aniline and the'whole stirred for one hour at between 90 and 95 C. The excess of aniline is distilled ofi after the addition of caustic soda solution by means of steam whereupon the anthraquinonedianil-B-sulphonic acid sodium salt separates out as a red precipitate.

It dissolves in dilute caustic alkali solution Emamplel I 1' part of pyridine and 2 parts of anhydrous aluminium chloride and lO'parts' of p-tohiidine are mixed with 1 part of anthraquinone, whereupon the whole is warmed fora short time at between and Then 035 part of zinc dust is gradually introduced into the reaction mixture which is again stirred for 1 hour at 80 C. 9.10di-p-t0luidoanthracene is obtained as a yellow red powder in a practically theoretical yield by pouring the reaction mixture in dilute acid.

Example 1!;

5 parts of anthraquinonedianil obtained as described in Liebi'gs Annalen, vol. 396, page 178, are dissolved in 100 parts of boiling amyl alcohol whereupon 3 parts of metallic sodium are added. The reduction is complete in a short time. The product thus obtained crystallizes from the reaction mixture on cooling. The product is identical with that obtained according toExam'plelQ.

EwampZe 15 4 parts of the dianil obtainedby condensation of 1-ohloranthraqumone and o-chloro-' aniline by means of aluminium chloride are.

to give a deep red solution.

1 part of the dianil-thus obtained is dissolved in from 5 to 10 parts of a dilute caustic soda solutionand reduced by means of sodium hydrosulphite while warming. The sodium saltof 9.10-dianilino anthracene-B-sulphonic acid thus obtained corresponds to the formula It is diflicultly soluble in water and caustic soda solution and dyes wool from an acid bath yellow shades.

5 parts of anthraquinonedianil are dissolved in 100 parts of concentrated sulphuric acid while cooling and reduced by means of 3 parts of copper powder. The reduction is completed in'a very short time. On'dilution of thereaction mixture by means of water the 9.10-dianilino anthrac'ene separates out.

What we claim is 1. Anthracene substltutlon products havmg the general structure: 1

in which X stands for hydrogen, or an acyl radicle of the lower fatty acid series, and Y for hydrogen or an acyl radicle of the lower fatty acid series or a radicle of the benzene series, in which last case X must he hydrogen,

which anthracene substitution products fluf oresce when exposed to ultra-Violet light and are readily decomposed to form anthraquinones.

2. Anthracene substitution products having the general structure:

in which Y stands for a radicle of the benzene series, which anthracene substitution products are colored compounds, fluoresce when exposed to ultra-Violet light and are readily decomposed to form anthra'quinones. 3. 9.10-dianalino anthracene corresponding to the formula:

crystallizing from organic solvents in yellow forming a yellow red powder, crystallizing rom organic solvents, fluorescent when exposed to ultra-violet light and decomposing to form anthraquinone when heated in 70 per cent sulphuric acid with an oxidizing agent.

5. 1-oh1or-9.lO-di-o-chloroanilino anthraoene corresponding to the formula:

crystallizingfrom amyl alcohol in brilliant yellow crystals, fluorescent when exposed to ultra-violet light and decomposing to form l-chloranthraquinone when heated in 7 0 per cent sulphuric acid with an oxidizing agent.

In testimony our hands. 7

MAX ALBERT KUNZ.

RUDOLF STROH. HERMANN DIMROTH.

whereof we have hereunto set 

